Production of low boiling hydrocarbons



July 20, 1937. H. w. sHELDoN RODUCTION 0F LOW BOILING HYDROCARBONS Filed Feb. 10, 1953 atented July 20, A1937 Y' UNITED STATES PRODUCTION or Low.` BolLlNG nrnnocannons Howard w.; suenan, naaaonaela, N. J., assignor to Hondry Process Corporation, Dover, Del., a corporation o! Delaware Application February 10, 1933, Serial No. 656,052

18 Claims. (CL. 196-52) This invention relates to the production of such products as benzine, gasoline', naphtha, kerosene and the like from higher boiling starting material-such as crude petroleum, or'fractions of the same, or oils from the destructive distillation of carbonaceous materials:

lOne object of the invention is to combine known methods of pyrolytic conversion of hydrocarbons with a catalytic process capable of continuous operation and in` which the contact mass is preferably regenerated in situ, .thereby to enhance certain advantagesinherent in the processes which are combined. Other objects will be apparent from thedetailed description which follows.

One concrete'.embodiment ofthe invention is of the accompanying drawing.

The` apparatus as disclosed comprises a catalytic system, indicated generally by reference character A, a pyrolytic system, indicated by B, and a viscosity breaking device C, all three adapted to be usedin combination to secure a high combined yield of low boiling hydrocabons,

such4 as gasoline, with a good antiknock rating. The use' of the viscosity breaker C, however, is optional, depending upon the type of starting material.

The catalytic system A conforms, in general,v

- to that `disclosed in the copending application of, Eugene J. Houdry,' Serial No. 610,567, filed May .11, 1932. It comprises a tubular heater la and two or more catalytic converters 2a containing catalytic material capable. of making the desred conversionsuch as a contact mass consisting of an activated hydrosilicate of aluminum, with or without the addition of active` metal oxides, preferably in molded form, as disclosed,

for example, in the copending application of Eugene J. Houdry, Serial No. 600,581, filed March 23, 1932, so as to be capable of regeneration in situ. The catalytic converters are arranged for lalternate operation on stream and in regeneration, thejvaporized ,products from heater la being fed thereto through a valved line 3a, at atmospheric orlow superatmospheric pressure and or known type, comprising a tubular heater lc arranged to bring the material to be treated to'a temperature of from 700 to 900 F., and having a discharge line 2c and a feed line 3c.

Two fractionating columns are used, namely la and 'lb and.,l as hereinbefore indicated, the `overhead or gasoline fractions from each may be f blended together to provide a high yield of high quality motor fuel. Line 4a: of the catalytic system' discharges into fractionator 1a, as indicated in the drawing, and the converted products issue from the top thereof through a line 8a, to be condensed `and stored or subjected to, a,l further- 'refningoperation The residual oil or recycle stock-which is thrown down in fractionator 1a is conducted from the bottom thereof by line 5b as feed for heater lb of the pyrolyt'ic system. Thestarting material or fresh feed to be converted, such as crude petroleum or a distillate,

.may be forcedb'y valved connections through either or both of trimming coils 9b and 9a in the tops of fractionators 'lb and 1a, respectively, for controlling the temperatures of the same, or may by-pass either or both ot such coils, as desired, is conducted by line I0 through heat exchangers i0a and I0b in vapor lines 4a and 4b, respectively, of the tvo converting systems, andis admitted in a preheated condition, at Il, into fractionator 1b. Under some conditions of operation, additional cooling of vapors in fractionators 'lb and use of open reflux or other conventional means. A tray I2b in the upper portion of fractionator 1b makes an upper cut of the material therein,

aff

v1a may be required and may be provided by the which is conducted by line i2a to serve as feed 1 for heater la of catalytic system A. A lower l tray |317 below fresh" feed inlet il takes a bottom cut from the feed and heavy fractions of the vline 4b of the pyrolyticsystem and line 2c 'of the viscosity breaker discharge, line 4b entering at' a4 point adjacent the bottom of the zone and line 2c discharging at a point intermediate the latter and tray |317. Optionally, an additional tray Mb intermediate lower tray l3b and upper tray I2b and @ve fresh feed inlet Il may be provided to make an intermediate cut which is conducted by valved line |5b to connect with feed line 5b leading to heater Ib of the pyrolytic system. A

- 'valved control IGb is provided for line lib such that when line lib is closed, the cut collected in tray Hb is drained into tray I3b by a branch Ilb. The converted vapors escape from the top of fractionator 1b through a line 8b, to be condensed and stored or refined as desired. Tarry residues are withdrawn fromvaporizing zone 1b' through 'an outlet connection lsb. Heavynaphtha may be collected and Withdrawn by a tray I9b near the top of` fractionator 1b.

From the above, it will be apparent that the side streams or. cuts forming the feeds to the heater of the catalytic system and to the viscosity breaker are made in the fractionator 1b intowhich the preheated fresh feed and the products of the pyrolytic system and 'of the viscosity breaker are discharged; that all the residual oil or recycle stock thrown down in fractionator 1a from catalytic system Ais conducted to the heater of pyrolytic system B as feed therefor; that, optionally, a side stream or cut intermediate the cuts for the catalytic system and `for the viscosity breaker4 may be taken from fractionator lb for the pyrolytic system, and that this cut may, if

desired, be mingled with the residual oil from the' catalytic system to make up the feed for the pyrolytic system; and that when viscosity breaking device C is not used, tray l3b, which makes the cut therefor, will beomitted. The present arrangement is Yhighly flexible, in that the viscosity breaker may be omitted, and that, if the be arranged to conform to that of the first or second pass of the catalytic system when operating normally, which passes give the best yields with the least deposit of contaminants in thecatalytic mass, and the entire apparatus may be adjusted to secure maximum conversion with a high octane rating. In particular, the arrangement provides a cracking stock for the pyrolytic system from I which it can make gasoline of high octane rating.

I claim as my invention:

1. The process of converting a high boiling com posite hydrocarbon charge comprising components which are substantiallyhigher boiling than gasoline by catalytic and pyrolytic operations functioning interdependently and simultaneously and continuously which comprises separating said charge linto at least two fractions of .different boiling and molecular weight ranges, a lower boiling fraction and a higher boiling fraction,heating one of said fractions without substantial pyrolytic conversion thereof and passing itin vapor phase through a coni-ined zone containing a solid adsorptive catalyst comprising activated hydrosilicate of alumina so as to effect a transformation of reaction issuing from each of the said confined zones to form a commercial motor fuel.

2. The process yof converting a high boiling composite hydroca bon charge comprising componentsvwhich are substantially higher boiling than gasoline by catalytic and pyrolytic opera tionsfunctioning interdependently and simultaneously and continuously which comprises sepl arating said charge into at least two fractions oi' different boiling and molecular weight ranges, a lower boiling fraction and a higher boiling fraction, heating one of said fractions without substantial pyrolytic conversion thereof and passing it in yapor phase through a confined zone containing a solid adsorptive catalyst comprising activated hydrosilicate of alumina so as to effect a transformation of such fraction to a substantial extent into components within the gasoline boilingrange, passing the other of said fractions through a second confined zone maintained under conditions capable of eiecting -a pyrolytic conversion thereof to a substantial extent into components within the gasoline boiling range, and passing a portion of the higher boiling components of the product issuing from the first-mentioned confined zone, comprising hydrocarbons higher boiling than gasoline, into the said second confined zone together with the aforesaid other of said fractions of the hydrocarbon charge.

3. The process of converting a high boiling composite hydrocarbon charge comprising components which are substantially higher boiling than gasoline by catalytic and pyrolytic operations functioning interdependently and simultaneously and continuously which comprises separating said charge into at least two fractions of 1 f ing than the said lower boiling fraction, heating said lower boiling fraction without substantial pyrolytic conversion thereof and feeding it in vapor phase through a confined zone containing a solid adsorptive catalyst comprising activated hydrosilicate of alumina so as to effect a transformation of said lower boiling fraction to a'substantial extent into components within the gasoline-boiling range, passing the aforesaid higher boiling fraction through asecond confined zone maintained under conditions capable of effecting a pyrolytic conversion of the same to a substantial extent .into components withinthe gasoline boiling range, and blending hydrocarbons inthe gasoline boiling range from products of reaction issuing from each of th said confined zones to form a commercial motor fuel.

4. A proces's of converting hydrocarbons by catalytic and pyrolytic means operating independently but -simultaneously and continuously which comprises heating, vaporizingl and separating the hydrocarbon starting material into a plurality of fractions in a fractionating zone,

subjectinga light fraction havinga higher boiling l range than gasoline to catalytic conversion, sep-l arating the products of the catalytic conversion into light hydrocarbons in the gasoline boiling range and a residual oil, subjecting a still higher boilingjraction from said fractionating zone with the residual oil from said catalytic conversion to pyrolytic conversion, and continuously fractionating the products of said pyrolytic conversion in said fractionating zone along with the ,hydrocarbon starting material into light hydrocarbons in the gasoline boiling-range and intd said plurality of fractions to secure said fractions higher boiling than gasoline.

5. A process of converting hydrocarbons by catalytic and pyrolytic means operating inde-- pendentlybut simultaneously and continuously which comprises heating, vaporizing and sepaucts, and continuously performing the above.

rating the hydrocarbon starting material into a plurality of `fractions in a fractionating zone, subjecting a light fraction having a higher'bo'il-4 ing range than gasoline -to catalytic conversion, separating the products of the catalytic conver-` sion into light hydrocarbons in the gasoline boiling range and a residual oil, subjecting the residual oil from said catalytic conversion to 'pyrolytic conversion, heating a still higher boiling fraction from `said fractionating rione to a moderate cracking temperature to break the viscosity of such fraction,v and continuously fractionating the products of'said pyrolytic conversion and of saidviscosity breaking operation in said i'rst named l than gasoline.

fractionating zone alongwith the hydrocarbon' starting material into vlight hydrocarbons in 4the gasoline boiling range and into said plurality of fractions to secure said fractions higher boiling 6. A process of converting hydrocarbonsy by catalytic and pyrolytic means operating independentlybut simultaneously and continuously which comprises heating, vaporizing and sepa# rating the hydrocarbon starting material intoa plurality of fractions in a fractionatingzone, subjecting a light fraction having a higher boiling range than gasoline to'catalytic-conversion, separating the products of the catalytic conversion intol light hydrocarbons in the-gasoline boiling range and a. residual oil, subjecting a still higher boiling fraction from said fractionating zone along with the residual oil from 'said catalytic conversion t'o pyrolytic'converslon, heating-a still -higheraoiling fractionfrom said' fractionating 4 "zone to a moderate cracking temperature to break the'viscosity of such fraction, and continuously fractionating the products 'of said pyrolytic conversion and of said viscosity breaking operation i in said first named fractionating:zone along with erate cracking temperature to break the viscosity ofrsuch fraction, separating theeproducts of the viscosity breaking operation int/o fractions corresponding to those'indicated above in the same fractionating zone and combining them with the fractions'from the continuously supplied hydrocarbon starting material, cataiytically transrating the products of said pyrolytic cracking into ve yfractions corresponding to those indicated above in said same fractionating zone and combining them with the fractions from thecontinu'ously supplied hydrocarbon starting material' and from the viscositybreaking' operation,i collectin'g the gasoline fractions from each of said separating steps as the desired low boiling prodsteps.

8. The process of converting hydrocarbons which comprises heating, vaporizing and fracionating hydrocarbon starting material in a primaryr fractionating zone, withdrawing an overing range, catalytically converting a higherboilving fraction at low pressure in4 the temperature range of 750 to 1000 F., fractionatihg the products of such conversion in a second fractionating zone to secure an overhead fraction in the gasoline boilingrange and a residual oil, pyrolytically converting theyresidualoil from saidzsecond frac-v Q tionating zone with the addition of a still higher boiling fraction from said primary fractionating zone, said pyrolytic conversion being eifected under high pressure and within the temperature range of 850 to 1100 F., 'and fractionating they products of said pyrolyti'c conversion in said prii mary fractionating zone along with said starting material thereby to augment the volume of the fractions obtainedtheren. 9. The process of converting hydrocarbons which comprises heating, vaporizing and fractionating hydrocarbon starting material in a primary fractionating zone, withdrawing anoverhead fraction from said zone in the gasoline boiling range, catalytically converting a higher boil- .ing fraction at low pressure inthe temperature range of 750 to 1000 F., fractionating the products of such conversion in a second fractionatingv soneto secure an overhead fraction in the gasoline boiling fange and a residual oil, pyrolytically converting the residual oil from ysaid second fractionating zone with the addition of astill higher boiling fraction from said primary fractionating zone, said pyrolytic conversion being enacted under high pressure and within the temperature boiling fraction from said primaryA fractionating zone to a temperature in the range of '100 to 900 F. to break the viscosity of such fraction, and

fractionating the products of said pyrolytic conl version and of said viscosity breaking operation in `55 range. of-850" to 1100 F., subjecting a still higher said primary fractionating zone along with said starting material thereby to augment the volume of the fractions'obtained therein.

' 10. An apparatus for the production of.low`

boiling hydrocarbons frpm high boiling hydrocarbons comprising means for heating hydrocar- -lbons to conversion temperatures, alternate catalytic regenerative 'converters adapted to contain pyrolytic heating means to the chamber, inde-4 take means on said column, means connecting the catalytic' converters to said' fractionating column,- a second Vaporizing and fractionating column, means connecting the time reaction chamber to the second column, means connecting the independent heating means to said second column, means for introducing charge oil into the second column, upper and'lower oitakes from said second column, means connecting the upper offtake to said first heating means, means connect.- ing the lower oiftake to said independent heating means, means connecting the bottom oii'- take of the rst column to the separate pyrolytic heating means, and vapor removing means connected' to the rst and second columns.

11. Anapparatus for the production of low boiling hydrocarbons from high boiling hydrocarbons comprising means for heating hydrocarbons to'converslon temperatures, alternate catalytic regenerative converters adapted to contain catalytic material, regenerative means,

` means for connecting the converters4 alternately to the hydrocarbon heating means and to the regenerative means, separate .means for heating hydrocarbons to pyrolytic conversion temperatures, a time reaction chamber, means connect-1 ing the separate pyrolytic heating means to the chamber, independent means for heating hydrocarbons to a moderate cracking temperature to reduce their viscosity, a fractionating column, a bottom oitake means on said column,N means connecting the catalytic converters to said fractionating column, a second vaporizing and fractionating column, means connectingthe time reaction chamber to the second column, means connecting the independent heating means to said second column, means for introducing charge oil into the second column, upper, lower and `intermediate offtakes from said second column, means connecting the upper oitakev -to saidJ rst heating means, means connecting the lower offtake to -said independent heating means, means connecting the bottom offta'ke of the flrst-column to the separate pyrolytic heating means, avalved connection from said intermediate oiftake to said separate pyrolytic heating means, and vapor re, moving means connected to said rst and second columns. e;

12. An apparatus for the production of low boiling hydrocarbons fromhigh boiling hydrocarbons comprising means for heating hydrocarbons to conversion temperatures, alternate catalytic regenerative converters adapted to contain catalytic material, regenerative means, means for connecting the converters alternately to the hydrocarbon heating means and toA the regenerative means, separate means for heating hydrocarbons to pyrolytic conversion temperatures, a time reaction chamber, means connecting the separate pyrolytic heating means to the chamber,I a fractionating column, bottom otake means on said column, means-connecting the 'catalytic converters to said fractionating column,

a valved connection from said lower oiftake to f tures, a time reaction chamber, means connecting the'v separate pyrolytic heating means to the chamber, independent means for heating hydrocarbons to a moderate cracking temperature to reduce their viscosity, a fractionating column, a

bottom `oitake means on said column, means connecting the catalytic converters to said fractionating column, a second vaporizing and fractionating column, means connecting the time reaction chamber to the second column, means connecting the independent heating means to said second column, means for introducing charge oil into the second column, upper and lower oitakes from said second column, means connecting the upper oitake to said rst heatingmeans, means connecting the lower oitake boiling Ahydrocarbons from high boiling hydrocarbons comprising means for heating hydrocarbons to conversion temperatures, alternate catalytic regenerative converters adapted to contain catalytic material, regenerative means, means for connecting the converters alternately to the hydrocarbon heating means and to the regenerative verters to said fractionating column, a second vaporizing and fractionating column, means connecting the time reaction chamber to-the second column, eans for introducing charge oil into said second'column, an oitake from said second column, means connecting said oitake to said rst heating means, means connecting the bottom 'oitake of the rst column to said separate pyrolytic heating means, and vapor removing means connected to said first and second columns, said chargev oil means entering said second column below said oitake and said connecting means fromsaid time reaction chamber entering said second column below said charge oil means.

15. An apparatus for the production of low boiling hydrocarbons from vhigh boiling hydrocarbons comprising means for heating hydrocarbons to conversion temperatures, alternate catalytic regenerative converters adapted to contain catalytic material, regenerative means, means for connecting the converters alternately to the hydrocarbon heating means and to the regenerative means, separate means for heating hydrocarbons to pyrolytic conversion temperatures, a time reaction chamber, means connecting the separate pyrolytic heating means to the chamber, in-

,dependent means for heating hydrocarbons to a moderate cracking temperature to reduce their viscosity, a fractionating column, a bottom oitake means on said column, means connecting the catalytic converters to said fractionating column, a second vaporizing and fractionating. column, means connecting the time reaction chamberto the second column, ,means connecting the independent heating means to said second column,

means for introducing charge oil into the second i column, upper, lower and intermediate offtakes from said second column, means connecting the upper oitake to said first heating meansmeans connecting the lower oitake to said independent heating means, means connecting the bottom offtake of the rst column to the separate pyrolytic heating means, a valved connection from said intermediate offtake to-said separate pyrolytic heating means, and vapor removing means connected to said first and second columns, saidcatalytic regenerative converters adapted to contain catalytic material, regenerative means, means for connecting the converters alternately to the hydrocarbon heating means and to the regenerative means. separate means for heating hydrocarbons to` pyrolytic conversion temperatures, a time reaction chamber, means connect-- ing the separate pyrolytic heating meansrto the y chamber, a fractionating column, a bottom otake means on said-Scolumn, means connecting the catalytic converters to said fractionating column, a second vaporizing and fractionating column, means connecting the time reaction chamber to the second column, means for introducing charge oil into said second column, upper andh lower offtakes from said second column, means connecting the upper offtake to said first heating means, means connecting the bottom offtake of the first column to said-separate pyrolytic heating4 means, a valved connection Vfrom said lower oitake to said last named\ heating means, and vapor, removing means connected to said iirst and second columns, said charge oil means entering said second column below said -lower oitake and said connecting means from said time reaction chamber entering said second column below said charge oil means.

17. An apparatus for the production of low boiling hydrocarbons from high boiling hydroa carbons comprising means for heating hydrocarbons to conversion temperatures, alternate catalytic regenerative converters adapted to 'contain catalytic, material, regenerative means, means for connecting the converters alternately to the hydrocarbon heating means and to the regenerative means, separate means for yheating hydrocarbons to pyrolytic conversion temperatures, a time reaction chamber, means connecting the separate pyrolytic heating means to the chamber, independent means for heating hydrocarbons toa moderate cracking temperature to reduce their viscosity, a fractionating column, a bottom oitake means on said column, means connecting the catalytic converters to said fractionating column, a second vaporizing and fractionating column, means connecting the time reaction chamber to the second column,.means connecting the independent heating means `to 'said second column, means for introducing charge oil into the second column, upper and lower oitakes from said second column, means connecting the upper ofltake to said rst heating` means, means connecting the lower oitake to said independent heating means, means connecting the' bottom oitake of the rst column to the separate pyrolytic heating means, and vapor removing means connected to the iirst and second columns, said connecting meansfrom said viscosity breaking means entering Asaid second column adjacent the bottom thereof While said connecting means from said time reaction chamber and said charge oil means e'nter said second column at successively higher levels. i

18. An apparatus for the production of low boiling hydrocarbons from high boiling hydro` carbons comprising means for heating hydrocarbons to conversion temperatures, alternate catalytic regenerative converters adapted to contain catalytic material, regenerative means, meansA for connecting the converters alternately to the hydrocarbon heating means and to the regenerative means, separate means for heating hy- Y drocarbons to pyrolytic conversion temperatures,

a time reaction chamber, means connecting the separate pyrolytic heating' means to the chamber, independent means for heating hydrocarhonsto a moderate cracking temperature to reduce .their viscosity, a fractionating column, a bottom offtake means'on said column, means connecting the catalytic converters to said fractionating column, a second vaporizing and fractionating column, means connecting the time reaction chamber to the second column, means connecting the independent heatingmeans to said second column, means for introducing charge oil into the second column, upper, lower and intermediate oiItakes from said second column, means connecting the upper oitake to said rst heating means,.means connecting the lower oitake to said independent heating means, means connecting the bottom oiltake of the first column to the'separate pyrolytic heating means, a valved connection from said intermediate offtake to said separate pyrolytic heating means, and vapor removing means connected to said irst and second columns, said connecting means from said viscosity breaking means entering said second column adjacent the bottom of the latter, while said connecting means from said time reaction chamber enters said second column somewhat above said viscosity breaking connection but below said lower oflt-ake, while said charge oil means enters said second column above said lower 

